Effect of Oxidized Starch on Morphology,Rheological and Tensile Properties of Low-Density Polyethylene/Linear Low-Density Polyethylene/Thermoplastic Oxidized Starch Blends

In this work, morphology, rheological and tensile properties of low-density polyethylene/linear low-density polyethylene/thermoplastic oxidized starch (LDPE/LLDPE/TPOS) blends are studied. The blends of LDPE/LLDPE (70/30, w/w) containing 0–20 wt% TPOS in the presence of 3 wt% of PE-grafted maleic anhydride (PE-g-MA) as a compatibilizer are prepared by a twin screw extruder and then converted to appropriate thin films using an extrusion film blowing machine. Scanning electron microscopic images show that there is a relative good dispersion of oxidized starch particles in PE matrices. However, as TPOS content in the blends increases, the starch particle size increases too. The rheological analyses indicate that TPOS can decrease the elasticity and viscosity of the blends. The LDPE/LLDPE/TPOS blends show power-law behavior and as the TPOS content increases the power-law exponent (n) and consistency index (K) decrease. The ultimate tensile strength and elongation at break of the final blend films reduce, when TPOS content increases from 5 to 20 wt%. However, the required mechanical properties for packaging applications are achieved when 10 wt% oxidized starch is added, according to ASTM D4635.     

A Biobased Blend of Cellulose Diacetate with Starch

Two bio-based polymers, cellulose diacetate (CDA) and starch, were used to prepare blends with reasonable properties and low cost. Due to the poor processing properties, starch was modified in the presence of glycerol and epoxidized soybean oil (ESO), and CDA was plasticized by triacetin (TA) and ESO, respectively. The morphologies of the blends with different amounts of modified starch (MST) were studied by scanning electron microscope (SEM), and the physical properties of the blends, including thermal stability, mechanical property, water and moisture resistance, were investigated. The equilibrium moisture absorption rates of the blends containing 30 and 50 wt% MST at 100 % of relative humidity(RH) were 9.4 and 15.0 %, respectively. SEM and DMA results demonstrated that CDA and MST had a certain extent of compatibility. Due to the partial plasticization of starch, the tensile strength of the blends was nearly not affected by the amount of MST. Even if 50 wt% MST was added, the tensile strength of the blend was as high as 24.7 MPa. The obtained blend containing 30 wt% MST can keep good mechanical properties at 50 % RH, and its tensile strength and elongation at break are 30.2 MPa and 3.6 %, respectively. All the results show that the CDA/MST blends have a potential as an environmental friendly material.     

Starch, Poly(lactic acid), and Poly(vinyl alcohol) Blends

Research on biodegradable materials has been stimulated due to concern regarding the persistence of plastic wastes. Blending starch with poly(lactic acid) (PLA) is one of the most promising efforts because starch is an abundant and cheap biopolymer and PLA is biodegradable with good mechanical properties. Poly(vinyl alcohol) (PVOH) contains unhydrolytic residual groups of poly(vinyl acetate) and also has good compatibility with starch. It was added to a starch and PLA blend (50:50, w/w) to enhance compatibility and improve mechanical properties. PVOH (M_W 6,000) at 10%, 20%, 30%, 40%, 50% (by weight) based on the total weight of starch and PLA, and 30% PVOH at various molecular weights (M_W 6,000, 25,000, 78,000, and 125,000 dalton) were added to starch/PLA blends. PVOH interacted with starch. At proportions greater than 30%, PVOH form a continuous phase with starch. Tensile strength of the starch/PLA blends increased as PVOH concentration increased up to 40% and decreased as PVOH molecular weight increased. The increasing molecular weight of PVOH slightly affected water absorption, but increasing PVOH concentration to 40% or 50% increased water absorption. Effects of moisture content on the starch/PLA/PVOH blend also were explored. The blend containing gelatinized starch had higher tensile strength. However, gelatinized starch also resulted in increased water absorption.     

Thermoplastic Blends from Albumin and Zein: Plastic Formation and Mechanical Properties Including Modeling

The use of proteins in blending with traditional polymers in the formation of thermoplastics can produce plastics with properties that are superior to traditional petroleum-based plastics. We investigated the physical and thermal properties of albumin and zein thermoplastic blends plasticized with glycerol and mixed with varying amounts of low-density polyethylene (LDPE). Several mechanical models were utilized to determine how tensile properties will be altered when varying amounts of protein/LDPE were added into the thermoplastic blend. When analyzed for thermal properties, we found that as the amount of LDPE in the thermoplastic blend increased, the resulting plastic possessed thermal properties that were more similar to pure LDPE plastics. In terms of mechanical properties, comparison between the experimental data and model predictions points to a synergistic effect between albumin and LDPE that leads to higher modulus, while a potential lack of compatibility between zein and LDPE leads to a plastic with lower modulus. Based on our results, the use of albumin and zein proteins when blended with LDPE in the production of thermoplastics has potential use in the areas of medical and food packaging applications.     

Evaluation of the Biodegradability of Polyvinyl Alcohol/Starch Blends: A Methodological Comparison of Environmentally Friendly Materials

Polyvinyl alcohol (PVA) and starch are both biodegradable polymers. These two polymers can be prepared as biodegradable plastics that are emerging as one of the environmental friendly materials available now. In this study, after reacting with sodium trimetaphosphate (STMP), modified corn starch was blended with PVA in different ratios by a barbender. Test samples were prepared for mechanical and thermal properties measurements. The surface roughness and morphology of fractured surface of the samples were observed by an atomic force microscopy (AFM) and scanning electron microscope (SEM) measurements. Aqueous degradation by enzyme, water absorption and biodegradability behavior were evaluated for the degradability. The biodegradability of these materials was followed by bio-reactivity kinetics models. Results showed that the addition of modified starch could enhance its water uptake. With an addition of 20 wt% of modified starch, the blend had a maximum weight loss during enzymatic degradation. It was found that the degradability was enhanced with the addition of the starch. Analyzing the results of the biodegradability based on the kinetic models, the growth rate of the microorganism was found to be increasing with the increase of the content of starch in the PVA/starch blends in the first order reaction fashion. In our biodegradability analysis, i.e., based on the China national standards (CNS) 14432 regulations, we estimated the decomposition behavior based on the mentioned first order reaction. We found that the PVA/starch blends would take 32.47, 16.20 and 12.47 years to degrade by 70% as their starch content 0, 20 and 40 wt%, respectively.     

Modification of Aliphatic Polyesters and Their Reactive Blends with Starch

Modified polycaprolactone was synthesized by melt reaction of PCL and reactive monomers such as glycidyl methacrylate (GMA) and maleic anhydride (MAH) in the presence of benzoyl peroxide in Brabender mixer. MAH showed a different grafting phenomenon compared to GMA. The reaction mechanism was discussed with different reactive monomers. Reactive blends of the PCL-g-GMA and the gelatinized starch with glycerin were prepared and their mechanical properties and biodegradabilities were investigated. Reactive blends of PCL-g-GMA and starch showed well-dispersed starch domain in the matrix and better mechanical strength than the unmodified PCL/starch blend. However, the reaction between PCL-g-GMA and starch induced a crosslinking during the reactive blending and this crosslinking in the blend lowered the biodegradation of the blend during the composting test. The biodegradability was investigated by the weight loss and surface morphology change of the blend in the composting medium.     

Preparation and Biodegradation of Starch/Polycaprolactone Films

Starch granules were modified with trisodium trimetaphosphate (TSTP) and characterized by P³¹-NMR, FTIR and DSC. Seventy-micron films were prepared from modified starch and polycaprolactone blends by solvent casting technique. Three different types of films—PCL (100% polycaprolactone), MOD-ST/PCL (50% modified starch and 50% polycaprolactone blend) and NONMOD-ST/PCL (50% nonmodified starch and 50% polycaprolactone blends)—were prepared, and their thermal, mechanical, and morphologic properties were investigated to show the increased performance of PCL with the addition of starch and also the effect of modification. It was observed that with the addition of starch the Young's modulus of polycaprolactone was increased and became less ductile, whereas tensile strength and elongation at break values decreased. Biodegradation of these films was inspected under different aerobic environments with the presence of Pseudomonas putida, activated sludge, and compost. It was observed that whereas P. putida had almost no effect on degradation during 90 days, with the presence of activated sludge, considerable deformation of films was observed even in the first 7 days of degradation. In a compost environment, degradation was even faster, and all polymer films were broken into pieces within first 7 days of degradation and no film remained after 15 days.     

Blending of Epoxidised Palm Oil with Epoxy Resin: The Effect on Morphology, Thermal and Mechanical Properties

Epoxy resin prepared by the reaction of a diglycidyl ether of bisphenol A (DGEBA) and m-xylylenediamine (m-XDA) was modified with 10% wt of epoxidized palm oil (EPO). The EPO was first pre-polymerized with m-XDA at various temperatures and reaction times. The resulting product was then mixed with the epoxy resin at 40?°C and allowed to react at 120?°C for another 3?h. The fully reacted DGEBA/m-XDA/EPO blend was characterized by using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal gravimetric analysis, tensile test, hardness indentation and dynamic mechanical analysis. The SEM study shows that different types of morphology, ranging from phase separated to miscible blends were obtained. A miscible blend was obtained when the m-XDA and EPO were reacted for more than 2?h. The results from DSC analysis show that the incorporation of EPO at 10% wt in the epoxy blend reduced the glass transition temperature (T _g). The lowered T _g and mechanical properties of the modified epoxy resins are caused by a reduction in crosslinking density and plasticizer effect.     

Processing and Properties of Mixtures of PHB-V with Post-consumer LDPE

Mixtures of poly-β-(hydroxybutyrate-co-valerate) PHB-V with virgin and post-consumer low density polyethylene (LDPE) were prepared by melt mixing in proportions of 100/0, 90/10, 80/20, 70/30 and 0/100 (wt/wt%). The mixtures were analysed by infrared spectroscopy, differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), melting flow index (MFI), tensile tests, scanning electron microscopy (SEM) and biodegradation in simulated soil. The DMTA and DSC curves of post-consumer LDPE suggested that this polymer was a mixture of LDPE and linear low density polyethylene (LLDPE). Virgin and post-consumer LDPE had lower MFI than PHB-V, but the blends showed higher index as the content of LDPE increased. The addition of LDPE reduced the tensile strength and Young’s modulus of the mixtures compared with PHB-V. SEM indicated poor interfacial adhesion between PHB-V and LDPE. PHB-V degraded slow and gradually, while both LDPE showed virtually no degradation under the conditions studied. The biodegradability of the blends depended on their composition and of the type of LDPE. LDPE improved the biodegradability of the mixtures.     

Effects of Modified Starch and Different Molecular Weight Polyvinyl Alcohols on Biodegradable Characteristics of Polyvinyl Alcohol/Starch Blends

The common biodegradable properties of polymer make them an excellent pair for blending, and the water solubility of polyvinyl alcohol (PVA) makes it easy to mix evenly with the starch. In this study, PVAs with different molecular weights were blended with various compositions of cross-linked starch (CLS) to explore the effects of molecular weight of PVA on the biodegradable characteristics of the PVA/starch blends. Comparing the biodegradability of all the various PVA/starch blends, a PVA was singled out from the PVA/starch blends of higher biodegradability. Further, the chosen PVA was then blended with the acid-modified starch (AMS) to systematically investigate the effects of the modified processing of starch on the biodegradable characteristics of the PVA/starch blends. Differential scanning calorimetry (DSC) analysis of PVA and PVA/starch specimens reveal that the T_m values of PVA/starch specimens reduce gradually as their CLS or AMS contents increase. After the CLS is blended in PVAs of different molecular weights, the tensile strength (??_f) and elongation at break (??_f) values of (P₁₀₀S₀)G₂₀M₁ specimen increase and simultaneously reduce, respectively, as their molecular weights of PVA increase from about 80,000 (PVA_BF-17) to 120,000 (PVA_BF-26). The ??_f and ??_f values of the PVA/modified-starch blends decrease with an increase in the modified starch contents. The ??_f values of the PVA/AMS specimens decrease with an increase in the concentrations of hydrochloric acid. Comparing the ??_f values of the PVA/CLS specimens with those of the PVA/AMS specimens, the ??_f values of the PVA/CLS specimens are better than those of the PVA/AMS specimens. On the contrary, the ??_f values of the PVA/AMS specimens are better than those of the PVA/CLS specimens. According to the biodegradability of all the PVA/starch blends, PVA with higher molecular weights displays higher biodegradability. The biodegradability of the PVA/modified-starch blends increase as the modified starch contents of the PVA/modified-starch blends increase. As evidenced by the results of the biodegradability test, the biodegradability of the PVA/modified-starch blends, therein PVA is blended with 1N AMS, shows better biodegradability. The result of bio-reaction kinetics experiment can evaluate the decomposition tendency of the PVA/starch blends up to any biodegradable rate under ambient environment. Using the kinetic model of the first order reaction, it is estimated that 16.20?years and 12.47?years will be needed for the PVA_BF-17/starch blends, containing 20 and 40% of CLS respectively, to be degraded up to 70% under ambient environment. In addition, it is 1.68?years for the PVA_BF-26 blends with the 40% 2N AMS under decomposition environment while it is 1.94?years for the 40% 1N AMS. Overall, the decomposition potential of PVA/AMS specimens is better than PVA/CLS specimens. Furthermore, the 1N(26P₆₀AS₄₀)₁₀₀G₂₀M₁ specimen is coincidence the biodegradable material criteria of Environmental Protection Administration (EPA) of Taiwan.     

Physical properties and biodegradability of blends containing poly(ε-caprolactone) and tropical starches

In order to assess feasibility of tropical starches (sago and cassava starches) as biodegradable plastic materials, blending with poly(-caprolactone) (PCL), a biodegradable polymer, was carried out. It was confirmed that the physical properties (tensile strength and elongation) of PCL/sago and PCL/cassava blends were similar to those of PCL/corn blend, suggesting that sago and cassava starches can also be blended with PCL for production of biodegradable plastic. However, the properties of all PCL/starch blends were still low compared with those of polyethylene. Enzymatic degradability evaluation showed that lipase degradation of PCL and-amylase degradation of starch increased as the starch content in the blend increased. Burial test of the blends for 1, 3, and 5 months was carried out and the rate of degradation of the PCL/sago blend was confirmed to be slower than those of PCL/corn and PCL/cassava blends. Observation of the film blends structure by scanning electron microscope revealed that the starch was dispersed in a PCL continuous phase. Furthermore, changes in the film surface before and after enyzme treatments were observed.     

Valorization of regenerated LDPE by blending with EPDM in the presence of peroxide

The present work aims to the valorization of regenerated low density polyethylene (LDPE) by blending with small quantities of ethylene-propylene-diene monomer (EPDM). Three types of regenerated LDPE (rLDPE) from different waste sources (greenhouses, milk pouches,...) were characterized in terms of physico-chemical (density, melt flow index, water absorption, melting temperature and structure by Fourier transform infrared (FTIR) spectroscopy) and mechanical properties (tensile properties and hardness). The optimization of the peroxide content required for the crosslinking of the LDPE/EPDM blends was due by measuring torque and tensile strength. Once the peroxide content was optimized, different blends were obtained by varying the EPDM content. Then they were characterized physically (density, water absorption) and mechanically (tensile properties and hardness). Finally, the blends behavior under the conjugated effect of heat and water was determined at 70 °C for 7 days. The obtained results showed that this kind of blending has contributed in improving the performance of regenerated LDPE.     

Poly(Ethylene Glycol) as a Compatibilizer for Poly(Lactic Acid)/Thermoplastic Starch Blends

A new route to prepare poly(lactic acid) (PLA)/thermoplastic starch (TPS) blends is described in this work using poly(ethylene glycol) (PEG), a non-toxic polymer, as a compatibilizer. The influence of PEG on the morphology and properties of PLA/TPS blends was studied. The blends were processed using a twin-screw micro-compounder and a micro-injector. The morphologies were analyzed by scanning and transmission electron microscopies and the material properties were evaluated by dynamic-mechanical, differential scanning calorimetry, thermogravimetric analysis and mechanical tests. PLA/TPS blends presented large TPS phase size distribution and low adhesion between phases which was responsible for the lower elastic modulus of this blend when compared to pure PLA. The addition of PEG resulted in the increase of PLA crystallization, due to its plasticizing effect, and improvement of the interfacial interaction between TPS and PLA matrix. Results show that incorporation of PEG increased the impact strength of the ternary blend and that the elastic modulus remained similar to the PLA/TPS blend.     

Lightweight Concrete Containing an Alkaline Resistant Starch-Based Aquagel

Starch aquagel-based lightweight concrete has properties similar to those of other lightweight concrete products. However, starch aquagels are unstable in the strongly alkaline conditions typical of Portland Cement-based concrete and may interfere with the setting process. The effect of alkali treatments on the physical, mechanical, and functional properties of starch aquagels and aquagels from starch/polymer blends was investigated. Starch was blended at 100–115°C in a twin-screw extruder with five different polymers to determine whether the blends improved alkaline resistance. Polymer blends containing 5%, 15%, and 30% of the polymer hydrated and formed aquagels when equilibrated in water for 24 h. However, equilibrium moisture content was lower for the blends compared to the starch control. Aquagels equilibrated in 0.15 N NaOH swelled, lost compressive strength and had greater than 90% moisture. The blend of starch and 30% PVOH absorbed less moisture and was more resistant to alkaline dissolution in 1 N NaOH than the other blends tested making it a more suitable material for aquagel-based concrete. The moisture content of starch-based aquagels and mixing time were critical factors in determining setting times. The size of aquagel blends had a minor effect on density and compressive strength.     

Anaerobic Biodegradation of Blends Based on Polyvinyl Alcohol

The presented work deals with blends composed of polyvinyl alcohol (PVA) and biopolymers (protein hydrolysate, starch, lignin). PVA does not belong to biologically inert plastics but its degradation rate (particularly under anaerobic conditions) is low. A potential solution to the issue problem lies in preparation of blends with readily degradable substrates. We studied degradation of blow-molded films made of commercial PVA and mentioned biopolymers in an aqueous anaerobic environment employing inoculation with digested activated sludge from the municipal wastewater treatment plant. Films prepared in the first experimental series were to be used for comparing biodegradation of blends modified with native or plasticized starch; in this case effect of plasticization was not proved. The degree of PVA degradation after modification with native or plasticized starch increases in a striking and practically same manner already at a starch level as low as approximately 5 wt.%. Films of the second experimental series were prepared as additionally modified with protein hydrolysate and lignin. Only lignin-modified samples exhibited a somewhat lower degree of biodegradation but regarding the measure of lignin present in blend this circumstance is not essential. Level of biodegradation with all discussed films differed only slightly—within range of experimental error.     

Effect of Nanoscale SiO<Subscript>2</Subscript> and TiO<Subscript>2</Subscript> as the Fillers on the Mechanical Properties and Aging Behavior of Linear Low-Density Polyethylene/Low-Density Polyethylene Blends

Linear low-density polyethylene (LLDPE) was blended with low-density polyethylene (LDPE) at a fixed ratio (80 wt LLDPE and 20 wt %LDPE) and filled with nanoparticles of SiO₂ and TiO₂ at a ratio up to wt 5%, so as to develop the polymeric composites suitable to preparing the agricultural micro-irrigation pipes having good environmental adaptability. These compounds were blended using calcium stearate, polyethylene wax, and titanate coupling agent as the auxiliary dispersants, and ethylene-vinyl acetate copolymer (EVA) as the toughness improver. The LLDPE/LDPE composites filled with the nanoparticles were extruded and injected to prepare the composites specimens for the performance evaluations and micro-irrigation pipe field test. The mechanical properties, thermostability, and processibility of the injected composites were investigated. The effect of heating in an oven and irradiating by ultraviolet on the mechanical properties of the composites was explored. The environmental adaptability of the micro-irrigation pipes made of the filled LLDPE/LDPE composites was evaluated making use of long-term outdoor field test in northwest China where the arid and harsh natural conditions are of great concerns. It was found that the LLDPE/LDPE blend with the LLDPE mass fraction fixed as 80% showed balanced mechanical and thermal properties and flexibility, and was suitable to be used as the basic resin matrix. The incorporation of nano-TiO₂ contributed to effectively improving the resistance to heating and ultraviolet irradiation of the composites. The composite made from 91% basic resin matrix, 6% EVA, and 3% mixed nano-SiO₂ and TiO₂, showed balanced comprehensive properties. The micro-irrigation pipes made of this filled LLDPE/LDPE composite had good environmental adaptability and service behavior in a three-year field test and were suitable to be used in arid area.     

Effect of Ionizing Radiation on the Morphological,Thermal and Mechanical Properties of Polyvinyl Alcohol/Polyethylene Glycol Blends

Blends of water—soluble polymers based on Poly vinyl alcohol (PVA) and Polyethylene glycol (PEG) have been prepared by the solution casting technique. The effect of various doses of γ-radiation on the structural properties of PVA/PEG polymer blends with all its compositions has been investigated. From the visual observation of all the blend compositions, it was found that, the best compatibility of the blend is up to 40% PVA/60%PEG. The structure–Property behavior of all the prepared blends before and after γ-irradiation was investigated by IR Spectroscopy, thermogravimetric analysis (TGA), mechanical properties and Scanning electron microscope (SEM). The gel content and the swelling behavior of the PVA/PEG blends were investigated. It was found that the gel content increases with increasing irradiation dose and PVA concentration in the blend. Swelling percent increased as the composition of PEG increased in the blend. The results obtained by FTIR analysis and SEM confirm the existence of possible interaction between PVA and PEG homopolymers. TGA of PVA/PEG blend, before and after γ-irradiation, showed that the unirradiated and irradiated PVA/PEG blends are more stable against thermal decomposition than pure PVA. Improvement in tensile mechanical properties of PVA/PEG blends was occurred.     

In Situ Compatibilization of Isotactic Polypropylene and High-Density Polyethylene by a Melt Cobranching Reaction

Incompatible polypropylene (PP) and polyethylene (PE) are difficult to separate in mixed recycling streams such as waste plastic packaging, which makes polyolefin mixtures unsuitable for high-quality products. In this work, based on the free radical branching reaction, a co-branching reaction of isotactic polypropylene (iPP) and high-density polyethylene (HDPE) blends was carried out in the presence of the peroxide, free radical regulator and multifunctional acrylate monomer, and a star-like long-chain branching (LCB) copolymer was obtained. The effect of in situ compatibilization on the structures and mechanical properties of iPP/HDPE was investigated, and the compatibilization mechanism was discussed. Results showed that the mechanical properties of the modified blends were largely improved, and efficient in-situ compatibilization of iPP and HDPE could be taken place in a wide process window. Moreover, the sizes of the dispersed phase in the modified blends were clearly decreased, and the interfacial thickness increased. Compared with the pure iPP/HDPE blend, the initial crystallization temperature of iPP in the modified iPP/HDPE blend was increased, and long branched chains of the LCB copolymers were physically entangled with the chemical identical homopolymers or even participated in the crystallization of iPP and HDPE. Thanks to the in situ compatibilization strategy, the compatibility of iPP/HDPE was significantly improved.

     

Effect of Poly(dioxolane) as Compatibilizer in Poly(ɛ-caprolactone)/Tapioca Starch Blends

The influence of poly(dioxolane) (PDXL), a poly(ethylene oxide-alt-methylene oxide), as compatibilizer on poly(ɛ-caprolactone) (PCL)/tapioca starch (TS) blends was studied. In order to facilitate blending; PCL, PDXL and TS must be blended together directly; so that PDXL is partially adhered at the TS surface as shown by scanning electron microscopy. The molecular weight effect of PDXL on the PCL/TS blends showed that mechanical properties of PCL/TS/PDXL blends from low molecular weight (M _n=10,000) and high molecular weight (M _n=200,000) PDXL were rather dependent on TS content. The enzymatic degradability of PCL/TS/PDXL blends using α-amylase increased as the TS content increased but was independent on the dispersion of tapioca starch in the PCL matrix.     

Dynamic Mechanical Behavior and Thermal Characterization of Biofilms Based on Starch Modified by Fungi Isolates

Starches modified by Ophiostoma spp. have been investigated to develop bio-materials with enhanced mechanical and physical properties for thermoplastic applications. In this study, glass transition temperature (T_g) of modified starches was investigated in both dynamic mechanical analyzer (DMA) and differential scanning calorimeter (DSC) to detect molecular changes in the starch’s structure. Overall, two thermal transitions were observed in modified starches, as opposed to one in their native counterparts. Scanning electron microscopy of granular modified starch indicated visible damages and internal structural perturbations in addition to occlusion of granular pores by extraneous materials owing to possible enzymatic degradation and production of secondary metabolites. Modified starches registered two-fold improvement in storage modulus as compared to that of native starches. From the study of second derivative of the mass loss against temperature, two thermal transitions were also identified in modified starches. X-ray diffraction analyses showed that crystalline regions of the starch granules remained intact after the modification. It is proposed that the second phase transition potentially corresponds to modified amylose fractions and/or exopolysaccharides produced by the fungi.